US4031436A - Electrolyte capacitors - Google Patents
Electrolyte capacitors Download PDFInfo
- Publication number
- US4031436A US4031436A US05/576,089 US57608975A US4031436A US 4031436 A US4031436 A US 4031436A US 57608975 A US57608975 A US 57608975A US 4031436 A US4031436 A US 4031436A
- Authority
- US
- United States
- Prior art keywords
- salt
- capacitor
- electrolyte
- acid
- silicotungstate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
Definitions
- This invention relates to electrolytic capacitors and more particularly, to a novel electrolyte comprising salts of heteropolyacids wherein the hetero atom is silicon, of the group consisting of silicotungstic acid and silicomolybdic acid.
- the use of heteropoly compounds wherein silicon is the heteropoly atom results in electrolytes having greater reliability at high temperature operation, 125° to 150° C. for example. Additionally, the electrolytes of the present invention result in capacitors having superior low temperature properties as compared to conventional electrolyte solutes, such as salts of organic acids, borates or borate complexes.
- a further object of the invention is to provide capacitor electrolyte as set forth above wherein the salt consists of ammonium, alkali metal, e.g. sodium, quaternary ammonium, or amine salts of the heteropolyacid, and the solvent consists of polar organic solvents.
- the salt consists of ammonium, alkali metal, e.g. sodium, quaternary ammonium, or amine salts of the heteropolyacid
- the solvent consists of polar organic solvents.
- the present invention contemplates the use of a novel electrolyte in a capacitor of conventional construction.
- a capacitor employs an aluminum foil anode and an aluminum foil cathode, separated by a paper spacer. After being wound into a cylindrical shape the foils and separator together with the electrolyte are sealed in a suitable container.
- the novel electrolyte of this invention consists essentially of a salt of silicotungstic acid (H 4 SiW 12 O 40 ) or silicomolybdic acid (H 4 SiMo 12 O 40 ) in a polar organic solvent.
- the formulas set forth in the preceeding sentence give the anhydrous compositions of the acids and are written so as to reflect the structure of the heteropoly anion which consists of a central Si atom surrounded by a W 12 O 40 (or Mo 12 O 40 ) cage.
- the cage is made up of linked WO 6 (or MoO 6 ) octahedra sharing oxygen atoms.
- silicotungstic acid is sold under the formula SiO 2 .sup.. 12WO 3 .sup.. 26H 2 O. This has the same stoichiometry as H 4 SiW 12 O.sub. 40.sup.. 24H 2 O, which is a hydrated form of silicotungstic acid. Although heating could reduce the number of associated water molecules to less than 24, this would not affect the chemical behavior because the functional part of the molecule would be unchanged.
- sodium silicomolybdate is available under the formula Na 4 [SiMo 12 O 40 ].
- x H 2 O when x is 10-15.
- the actual value of x is unimportant since the water content can be lowered if necessary by drying, or water can be added to the final electrolyte if that should be desirable.
- the alkali metals e.g. sodium, or ammonium quaternary ammonium or amine salts, either prepared in situ in the solution, or added to the solution as such.
- the solvent may be any of the commonly employed polar organic solvents employed in electrolytic capacitors. Examples of suitable solvents which may be employed are dimethylformamide, N-methylformamide, butyrolactone, N-methylpyrrolidone, dimethylsulfoxide, ethylene cyanohydrin, ethylene glycol, monomethyl ether of ethylene glycol and monoethyl ether of ethylene glycol.
- Electrolytes were prepared as follows:
- Electrolyte A is an electrolyte which is an embodiment of the present invention
- electrolyte B was prepared according to the teaching of the Hand U.S. Pat. No. 3,502,947.
- the electrolyte of the present invention has a lower dissipation factor at low temperatures which will result in superior low temperature performance.
- An anodic oxide film was formed on an aluminum foil coupon immersed in electrolyte C of Example 2.
- the current was held constant at a current density of about 0.5 ma/cm 2 and the temperature was about 25° C.
- the voltage rose smoothly at a constant rate up to 207V, at which voltage breakdown commenced.
- the electrolyte was then kept in a sealed container at 150° C for 545 hours. It was then cooled to room temperature and another aluminum coupon was anodically oxidized in this electrolyte at the same conditions as used initially. The voltage again rose smoothly at a constant rate to 216V at which point breakdown commenced.
- prolonged exposure at 150° C had no adverse effect on the oxide formation ability of this electrolyte. It was also observed that this exposure caused no change in appearance of the electrolyte nor produced any gas pressure, as might be caused by chemical decomposition, in the sealed container.
- An electrolyte (E) was prepared consisting of 2.81 g benzyltrimethylammonium silicotungstate dissolved in 8.7 ml dimethylformamide and 9.1 ml butyrolactone. The resistivity was 429 ohm-cm. After being heated at 125° C for 16 hours and then being cooled to room temperature, the resistivity was found to be 400 ohm-cm, less than a 7% change. In this electrolyte an aluminum coupon was anodized to 198V before breakdown commenced.
- Electrolyte F 0.06 molal solution of trimethylamine salt
- Electrolyte G 0.08 molal solution of triethylamine salt
- Example 2 The electrolytes were employed in test capacitors as set forth in Example 2 except that capacitors with 22 volt anode foil were used instead of the 140 volt anode foil as in Example 2. The tests were run at 150° C at a 10 volt applied load.
- the concentration of the heteropolyacid salts employed in this invention may range from (1) a lower limit determined by excessively high resistivity due to dilute electrolyte and the onset of corrosion due to trace impurities, to (2) an upper limit wherein there is little further decrease in resistivity with additional increase in concentration.
- concentration limits In the case of dimethylformamide solutions the suitable concentration limits have been found to be 0.02 to 0.20 molal and this range is satisfactory for the other polar solvents as well.
- the pH of the solutions have not needed any adjustment.
- the pH of amine salts in dimethylformamide ranges from about 5.7 to about 7.2.
- Aluminum oxide is not significantly attacked in the range of pH 5-7 and the heteropoly anion is more stable at low pH. Accordingly, the pH range may vary from about pH 5 to about 7.2, as measured with a glass electrode vs a conventional saturated calomel electrode as reference electrode.
Abstract
An electrolyte composition for electrolytic capacitors consisting essentially of a salt of a slilcotungstatic or silicomolybdic acid in a polar organic solvent and having a pH of from about 5.0 to about 7.2; and a capacitor containing said composition.
Description
This invention relates to electrolytic capacitors and more particularly, to a novel electrolyte comprising salts of heteropolyacids wherein the hetero atom is silicon, of the group consisting of silicotungstic acid and silicomolybdic acid.
The prior patent to Hand, U.S. Pat. No. 3,502,947, describes a capacitor electrolyte consisting of a heteropolyacid such as phosphotungstic acid, in a suitable organic solvent, such as N-N'-dimethyl formamide, neutralized with ammonia to a pH of 7.7. Greater stability is alleged over wide temperature ranges, long shelf life and a low current leakage.
In the present invention, the use of heteropoly compounds wherein silicon is the heteropoly atom results in electrolytes having greater reliability at high temperature operation, 125° to 150° C. for example. Additionally, the electrolytes of the present invention result in capacitors having superior low temperature properties as compared to conventional electrolyte solutes, such as salts of organic acids, borates or borate complexes.
It is an object of this invention to provide a capacitor having long shelf life, superior reliability at high temperature operation and superior low temperature properties, the said capacitor having an electrolyte comprising a silicotungstate or silicomolybdate salt in an organic solvent.
A further object of the invention is to provide capacitor electrolyte as set forth above wherein the salt consists of ammonium, alkali metal, e.g. sodium, quaternary ammonium, or amine salts of the heteropolyacid, and the solvent consists of polar organic solvents.
Further objects will become apparent from the following specification and claims.
The present invention contemplates the use of a novel electrolyte in a capacitor of conventional construction. Such capacitor employs an aluminum foil anode and an aluminum foil cathode, separated by a paper spacer. After being wound into a cylindrical shape the foils and separator together with the electrolyte are sealed in a suitable container.
The novel electrolyte of this invention consists essentially of a salt of silicotungstic acid (H4 SiW12 O40) or silicomolybdic acid (H4 SiMo12 O40) in a polar organic solvent. The formulas set forth in the preceeding sentence give the anhydrous compositions of the acids and are written so as to reflect the structure of the heteropoly anion which consists of a central Si atom surrounded by a W12 O40 (or Mo12 O40) cage. The cage is made up of linked WO6 (or MoO6) octahedra sharing oxygen atoms.
Commercial silicotungstic acid is sold under the formula SiO2.sup.. 12WO3.sup.. 26H2 O. This has the same stoichiometry as H4 SiW12 O.sub. 40.sup.. 24H2 O, which is a hydrated form of silicotungstic acid. Although heating could reduce the number of associated water molecules to less than 24, this would not affect the chemical behavior because the functional part of the molecule would be unchanged.
Similarly, sodium silicomolybdate is available under the formula Na4 [SiMo12 O40 ]. x H2 O, when x is 10-15. For the purposes of this invention the actual value of x is unimportant since the water content can be lowered if necessary by drying, or water can be added to the final electrolyte if that should be desirable.
The description of the acids as H2 SiW12 O40 and H4 SiMo12 O40 herein is not intended to limit them to the anhydrous form, but is to be understood as including their respective hydrated forms as well. Also, the terms "silicotungstate" and "silicomolybdate" refer to anions [SiW12 O40 ]- 4 and [SiMo12 O40 ]- 4 respectively, regardless of the formulas which may be employed by chemical suppliers as a result of past tradition and practice.
As salts there may be employed the alkali metals, e.g. sodium, or ammonium quaternary ammonium or amine salts, either prepared in situ in the solution, or added to the solution as such. The solvent may be any of the commonly employed polar organic solvents employed in electrolytic capacitors. Examples of suitable solvents which may be employed are dimethylformamide, N-methylformamide, butyrolactone, N-methylpyrrolidone, dimethylsulfoxide, ethylene cyanohydrin, ethylene glycol, monomethyl ether of ethylene glycol and monoethyl ether of ethylene glycol.
The invention will be further illustrated in the following examples:
Electrolytes were prepared as follows:
______________________________________ Electrolyte A sodium silicomolybdate 27 g dimethylformamide 100 g Electrolyte B phosphomolybdic acid 13 g triethylamine 1.4 ml (to give pH of 7) dimethylformamide 100 g ______________________________________
Electrolyte A is an electrolyte which is an embodiment of the present invention; electrolyte B was prepared according to the teaching of the Hand U.S. Pat. No. 3,502,947.
Both solutions were kept at 125° C for 310 hours. The initial and final resistivities (measured at 25° C) were as follows:
______________________________________ Resistivity (ohm-cm) Electrolyte Initial Reading Final Reading ______________________________________ A 117 115 B 160 282 ______________________________________
From the above test results, it is apparent that the resistivity of the silicomolybdate electrolyte was substantially unchanged whereas the prior art phosphomolybdate electrolyte underwent a 76% increase in resistivity under the same conditions.
Two electrolytes were prepared as follows:
______________________________________ Electrolyte C Triethylamine silicotungstate added to dimethyl- formamide to make a 100 g/liter solution Electrolyte D phthalic acid 24.9 g boric acid 1.5 g triethylamine 11.4 g dimethylformamide 100 g water 1 g ______________________________________
Two sets of capacitors were assembled using 140 V etched aluminum anode foil, cathode foil, and paper spacer, all being 2.0 cm wide and 15.2 cm long. One set was impregnated with electrolyte C and the other with electrolyte D, a typical prior art electrolyte. The dissipation factors measured at various temperatures were as follows:
______________________________________ % Dissipation Factor Temperature Electrolyte +25° C -40° C -55° C -70° C ______________________________________ C 3.3 10.5 13.7 32.2 D 2.2 11.6 21.8 99.1 ______________________________________
It is apparent that the electrolyte of the present invention has a lower dissipation factor at low temperatures which will result in superior low temperature performance.
An anodic oxide film was formed on an aluminum foil coupon immersed in electrolyte C of Example 2. The current was held constant at a current density of about 0.5 ma/cm2 and the temperature was about 25° C. The voltage rose smoothly at a constant rate up to 207V, at which voltage breakdown commenced. The electrolyte was then kept in a sealed container at 150° C for 545 hours. It was then cooled to room temperature and another aluminum coupon was anodically oxidized in this electrolyte at the same conditions as used initially. The voltage again rose smoothly at a constant rate to 216V at which point breakdown commenced. Thus, prolonged exposure at 150° C had no adverse effect on the oxide formation ability of this electrolyte. It was also observed that this exposure caused no change in appearance of the electrolyte nor produced any gas pressure, as might be caused by chemical decomposition, in the sealed container.
An electrolyte (E) was prepared consisting of 2.81 g benzyltrimethylammonium silicotungstate dissolved in 8.7 ml dimethylformamide and 9.1 ml butyrolactone. The resistivity was 429 ohm-cm. After being heated at 125° C for 16 hours and then being cooled to room temperature, the resistivity was found to be 400 ohm-cm, less than a 7% change. In this electrolyte an aluminum coupon was anodized to 198V before breakdown commenced.
Test results on two specific silicotungstate/dimethylformamide electrolyte solutions are as follows:
Electrolyte F = 0.06 molal solution of trimethylamine salt
Electrolyte G = 0.08 molal solution of triethylamine salt
The electrolytes were employed in test capacitors as set forth in Example 2 except that capacitors with 22 volt anode foil were used instead of the 140 volt anode foil as in Example 2. The tests were run at 150° C at a 10 volt applied load.
__________________________________________________________________________ Leakage Dissipation Current Capacitance Factor (micro- Electrolyte Hours No. Tested (microfarads) % DF amperes) __________________________________________________________________________ F 0 8 546 11.2 7.5 572 8 506 10.7 0.4 G 0 8 547 12.0 9.4 572 8 516 8.8 0.7 __________________________________________________________________________
To determine the effect of water in the electrolyte on capacitor performance, a test was made on 50 V capacitors of aluminum foil anode and cathode having spacing paper therebetween. The electrolyte consisted of electrolyte F (see Example 5) containing 2% water. The capacitors were kept at 50 V at 150° C. No effect on performance was noted after 328 hours on test. Thus, a small amount of water was shown to have no adverse results.
The concentration of the heteropolyacid salts employed in this invention may range from (1) a lower limit determined by excessively high resistivity due to dilute electrolyte and the onset of corrosion due to trace impurities, to (2) an upper limit wherein there is little further decrease in resistivity with additional increase in concentration. In the case of dimethylformamide solutions the suitable concentration limits have been found to be 0.02 to 0.20 molal and this range is satisfactory for the other polar solvents as well.
In practice, the pH of the solutions have not needed any adjustment. The pH of amine salts in dimethylformamide ranges from about 5.7 to about 7.2. Aluminum oxide is not significantly attacked in the range of pH 5-7 and the heteropoly anion is more stable at low pH. Accordingly, the pH range may vary from about pH 5 to about 7.2, as measured with a glass electrode vs a conventional saturated calomel electrode as reference electrode.
Claims (9)
1. A capacitor comprising aluminum anode and cathode members separated by an insulating spacer impregnated with an electrolyte consisting essentially of a solute of a salt of a heteropoly acid of the class consisting of silicotungstic acid and silicomolybdic acid in a polar organic solvent, said salt being selected from the group consisting of alkali metal, ammonium, quaternary ammonium and amine salts, and said electrolyte having a pH of about 5 to about 7.2, said acid containing 1 silicon atom per 12 atoms of tungsten or molybdenum.
2. The capacitor of claim 1 wherein the heteropoly acid salt has a molal concentration of about 0.02 to 0.20 in said polar solvent.
3. The capacitor of claim 2 wherein the salt is trimethylamine silicotungstate.
4. The capacitor of claim 2 wherein the salt is triethylamine silicotungstate.
5. The capacitor of claim 2 wherein the polar organic solvent is dimethylformamide.
6. The capacitor of claim 1 wherein said salt is an alkali metal salt.
7. The capacitor of claim 1 wherein said salt is a quaternary ammonium salt.
8. The capacitor of claim 1 wherein said heteropoly acid is silicotungstic acid.
9. The capacitor of claim 1, wherein said salt is an amine salt.
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US05/576,089 US4031436A (en) | 1975-05-09 | 1975-05-09 | Electrolyte capacitors |
CA249,879A CA1072316A (en) | 1975-05-09 | 1976-04-08 | Electrolytic capacitor |
GB16893/76A GB1507777A (en) | 1975-05-09 | 1976-04-26 | Electrolytic capacitors |
DE2618616A DE2618616C3 (en) | 1975-05-09 | 1976-04-28 | Electrolyte for electrolytic capacitors |
JP51050075A JPS5918854B2 (en) | 1975-05-09 | 1976-05-04 | Electrolytic capacitor and its electrolyte |
IT49317/76A IT1061638B (en) | 1975-05-09 | 1976-05-04 | IMPROVEMENT IN ELECTROLYTIC CAPACITORS |
FR7613866A FR2310623A1 (en) | 1975-05-09 | 1976-05-07 | ELECTROLYTE AND ELECTROLYTIC CONDENSER |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US05/576,089 US4031436A (en) | 1975-05-09 | 1975-05-09 | Electrolyte capacitors |
Publications (1)
Publication Number | Publication Date |
---|---|
US4031436A true US4031436A (en) | 1977-06-21 |
Family
ID=24302938
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US05/576,089 Expired - Lifetime US4031436A (en) | 1975-05-09 | 1975-05-09 | Electrolyte capacitors |
Country Status (7)
Country | Link |
---|---|
US (1) | US4031436A (en) |
JP (1) | JPS5918854B2 (en) |
CA (1) | CA1072316A (en) |
DE (1) | DE2618616C3 (en) |
FR (1) | FR2310623A1 (en) |
GB (1) | GB1507777A (en) |
IT (1) | IT1061638B (en) |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2822491A1 (en) * | 1978-05-23 | 1979-11-29 | Roederstein & Tuerk Kg | Electrolyte for low ohmic capacitor based on organic solvent - contg. ionogen also contains phosphoric acid and vanadate, molybdate and/or tungstate (NL 27.11.79) |
US4245278A (en) * | 1979-03-21 | 1981-01-13 | Sprague Electric Company | Electrolytic capacitor containing a metatungstate electrolyte |
US4376713A (en) * | 1977-12-21 | 1983-03-15 | Sprague Electric Company | AC Electrolytic capacitor electrolyte |
US4774011A (en) * | 1986-05-20 | 1988-09-27 | Mitsubishi Petrochemical Co., Ltd. | Electrolyte for aluminum electrolytic capacitor |
US4786429A (en) * | 1986-06-20 | 1988-11-22 | Mitsubishi Petrochemical Co., Ltd. | Electrolyte for aluminum electrolytic capacitor |
DE3930310C1 (en) * | 1989-09-11 | 1991-01-10 | Roederstein Spezialfabriken Fuer Bauelemente Der Elektronik Und Kondensatoren Der Starkstromtechnik Gmbh, 8300 Landshut, De | Electrolyte for electrolytic capacitor - comprises polar organic solvent contg. hetero-poly-acid e.g. tungsto-phosphoric acid or molybdo-silicic acid, etc. |
US5847920A (en) * | 1997-09-25 | 1998-12-08 | Motorola, Inc. | Electrochemical capacitor with hybrid polymer polyacid electrolyte |
US5986878A (en) * | 1997-09-25 | 1999-11-16 | Motorola, Inc. | Electrochemical capacitor with solid electrolyte |
US20070211413A1 (en) * | 2006-03-09 | 2007-09-13 | Avx Corporation | Wet electrolytic capacitor containing a cathode coating |
US20070211412A1 (en) * | 2006-03-09 | 2007-09-13 | Avx Corporation | Wet electrolytic capacitor |
US20080232031A1 (en) * | 2007-03-20 | 2008-09-25 | Avx Corporation | Cathode coating for a wet electrolytic capacitor |
US20080232030A1 (en) * | 2007-03-20 | 2008-09-25 | Avx Corporation | Wet electrolytic capacitor containing a plurality of thin powder-formed anodes |
US20080232029A1 (en) * | 2007-03-20 | 2008-09-25 | Avx Corporation | Neutral electrolyte for a wet electrolytic capacitor |
US20090303664A1 (en) * | 2005-11-15 | 2009-12-10 | Nippon Chemi-Con Corporation | Electrolytic capacitor |
US20100238606A1 (en) * | 2009-03-23 | 2010-09-23 | Avx Corporation | Electric Double layer Capacitor |
US20100238608A1 (en) * | 2009-03-23 | 2010-09-23 | Avx Corporation | Electrolytic Capacitor Containing a Liquid Electrolyte |
CN101236841B (en) * | 2008-01-11 | 2010-12-01 | 上海纳晶科技有限公司 | An electric chemical super capacitor making method |
CN102290599A (en) * | 2010-06-18 | 2011-12-21 | 索尼公司 | Noaqueous electrolyte and nonaqueous electrolyte battery |
CN103325580A (en) * | 2012-03-22 | 2013-09-25 | 波音公司 | Redox polymer energy storage system |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62114207A (en) * | 1985-11-14 | 1987-05-26 | 旭硝子株式会社 | Electrolyte for driving electrolytic capacitor |
WO2010058776A1 (en) * | 2008-11-19 | 2010-05-27 | 日産化学工業株式会社 | Charge-transporting material and charge-transporting varnish |
Citations (5)
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US2014169A (en) * | 1930-11-13 | 1935-09-10 | Robert T Mack | Filming metal for condensers |
US2890394A (en) * | 1955-04-13 | 1959-06-09 | Gen Electric | Electrolyte for electrolytic capacitors |
US3202611A (en) * | 1962-12-13 | 1965-08-24 | Itt | Capacitor electrolyte |
US3403305A (en) * | 1966-11-10 | 1968-09-24 | Sprague Electric Co | Electrolytic capacitor having an electrolyte containing a borate coordination compound |
US3502947A (en) * | 1967-01-23 | 1970-03-24 | Sangamo Electric Co | Electrolytic capacitor and novel electrolyte |
-
1975
- 1975-05-09 US US05/576,089 patent/US4031436A/en not_active Expired - Lifetime
-
1976
- 1976-04-08 CA CA249,879A patent/CA1072316A/en not_active Expired
- 1976-04-26 GB GB16893/76A patent/GB1507777A/en not_active Expired
- 1976-04-28 DE DE2618616A patent/DE2618616C3/en not_active Expired
- 1976-05-04 JP JP51050075A patent/JPS5918854B2/en not_active Expired
- 1976-05-04 IT IT49317/76A patent/IT1061638B/en active
- 1976-05-07 FR FR7613866A patent/FR2310623A1/en active Granted
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US2014169A (en) * | 1930-11-13 | 1935-09-10 | Robert T Mack | Filming metal for condensers |
US2890394A (en) * | 1955-04-13 | 1959-06-09 | Gen Electric | Electrolyte for electrolytic capacitors |
US3202611A (en) * | 1962-12-13 | 1965-08-24 | Itt | Capacitor electrolyte |
US3403305A (en) * | 1966-11-10 | 1968-09-24 | Sprague Electric Co | Electrolytic capacitor having an electrolyte containing a borate coordination compound |
US3502947A (en) * | 1967-01-23 | 1970-03-24 | Sangamo Electric Co | Electrolytic capacitor and novel electrolyte |
Non-Patent Citations (2)
Title |
---|
Maslov et al., "Chem Abstracts", vol. 77, 1972, 156919g. * |
Neimark et al., "Chem Abstracts", vol. 72, 1970, 137054b. * |
Cited By (31)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4376713A (en) * | 1977-12-21 | 1983-03-15 | Sprague Electric Company | AC Electrolytic capacitor electrolyte |
DE2822491A1 (en) * | 1978-05-23 | 1979-11-29 | Roederstein & Tuerk Kg | Electrolyte for low ohmic capacitor based on organic solvent - contg. ionogen also contains phosphoric acid and vanadate, molybdate and/or tungstate (NL 27.11.79) |
US4245278A (en) * | 1979-03-21 | 1981-01-13 | Sprague Electric Company | Electrolytic capacitor containing a metatungstate electrolyte |
US4774011A (en) * | 1986-05-20 | 1988-09-27 | Mitsubishi Petrochemical Co., Ltd. | Electrolyte for aluminum electrolytic capacitor |
US4786429A (en) * | 1986-06-20 | 1988-11-22 | Mitsubishi Petrochemical Co., Ltd. | Electrolyte for aluminum electrolytic capacitor |
DE3930310C1 (en) * | 1989-09-11 | 1991-01-10 | Roederstein Spezialfabriken Fuer Bauelemente Der Elektronik Und Kondensatoren Der Starkstromtechnik Gmbh, 8300 Landshut, De | Electrolyte for electrolytic capacitor - comprises polar organic solvent contg. hetero-poly-acid e.g. tungsto-phosphoric acid or molybdo-silicic acid, etc. |
US5847920A (en) * | 1997-09-25 | 1998-12-08 | Motorola, Inc. | Electrochemical capacitor with hybrid polymer polyacid electrolyte |
US5986878A (en) * | 1997-09-25 | 1999-11-16 | Motorola, Inc. | Electrochemical capacitor with solid electrolyte |
US9627145B2 (en) | 2005-11-15 | 2017-04-18 | Nippon Chemi-Con Corporation | Electrolytic capacitor for use in a charge/discharge circuit with shorter period and greater voltage difference |
US20090303664A1 (en) * | 2005-11-15 | 2009-12-10 | Nippon Chemi-Con Corporation | Electrolytic capacitor |
US7480130B2 (en) | 2006-03-09 | 2009-01-20 | Avx Corporation | Wet electrolytic capacitor |
US7511943B2 (en) | 2006-03-09 | 2009-03-31 | Avx Corporation | Wet electrolytic capacitor containing a cathode coating |
US20070211412A1 (en) * | 2006-03-09 | 2007-09-13 | Avx Corporation | Wet electrolytic capacitor |
US20070211413A1 (en) * | 2006-03-09 | 2007-09-13 | Avx Corporation | Wet electrolytic capacitor containing a cathode coating |
US20080232030A1 (en) * | 2007-03-20 | 2008-09-25 | Avx Corporation | Wet electrolytic capacitor containing a plurality of thin powder-formed anodes |
US20080232029A1 (en) * | 2007-03-20 | 2008-09-25 | Avx Corporation | Neutral electrolyte for a wet electrolytic capacitor |
US7460356B2 (en) | 2007-03-20 | 2008-12-02 | Avx Corporation | Neutral electrolyte for a wet electrolytic capacitor |
US20080232031A1 (en) * | 2007-03-20 | 2008-09-25 | Avx Corporation | Cathode coating for a wet electrolytic capacitor |
US7554792B2 (en) | 2007-03-20 | 2009-06-30 | Avx Corporation | Cathode coating for a wet electrolytic capacitor |
US7649730B2 (en) | 2007-03-20 | 2010-01-19 | Avx Corporation | Wet electrolytic capacitor containing a plurality of thin powder-formed anodes |
CN101236841B (en) * | 2008-01-11 | 2010-12-01 | 上海纳晶科技有限公司 | An electric chemical super capacitor making method |
US20100238608A1 (en) * | 2009-03-23 | 2010-09-23 | Avx Corporation | Electrolytic Capacitor Containing a Liquid Electrolyte |
US8223473B2 (en) | 2009-03-23 | 2012-07-17 | Avx Corporation | Electrolytic capacitor containing a liquid electrolyte |
US20100238606A1 (en) * | 2009-03-23 | 2010-09-23 | Avx Corporation | Electric Double layer Capacitor |
CN102290599A (en) * | 2010-06-18 | 2011-12-21 | 索尼公司 | Noaqueous electrolyte and nonaqueous electrolyte battery |
US20110311885A1 (en) * | 2010-06-18 | 2011-12-22 | Sony Corporation | Nonaqueous electrolyte and nonaqueous electrolyte battery |
CN103325580A (en) * | 2012-03-22 | 2013-09-25 | 波音公司 | Redox polymer energy storage system |
US20130250484A1 (en) * | 2012-03-22 | 2013-09-26 | Patrick John Kinlen | Redox Polymer Energy Storage System |
US9325041B2 (en) * | 2012-03-22 | 2016-04-26 | The Boeing Company | Redox polymer energy storage system |
US9728346B2 (en) | 2012-03-22 | 2017-08-08 | The Boeing Company | Redox polymer energy storage system |
CN103325580B (en) * | 2012-03-22 | 2017-08-18 | 波音公司 | redox polymer energy storage system |
Also Published As
Publication number | Publication date |
---|---|
IT1061638B (en) | 1983-04-30 |
DE2618616A1 (en) | 1976-11-18 |
FR2310623A1 (en) | 1976-12-03 |
GB1507777A (en) | 1978-04-19 |
JPS51140161A (en) | 1976-12-02 |
CA1072316A (en) | 1980-02-26 |
JPS5918854B2 (en) | 1984-05-01 |
DE2618616B2 (en) | 1978-10-19 |
DE2618616C3 (en) | 1979-07-05 |
FR2310623B1 (en) | 1981-10-09 |
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